High-sensitivity differential scanning calorimetry for measurement of steroid entrapment in nebulised liposomes generated from proliposomes

A novel approach to the determination of steroid entrapment in the bilayers of aerosolised liposomes has been introduced using high-sensitivity differential scanning calorimetry (DSC). Proliposomes were dispersed in water within an air-jet nebuliser and the energy produced during atomisation was used to hydrate the proliposomes and generate liposome aerosols. Proliposomes that included the steroid beclometasone dipropionate (BDP) produced lower aerosol and lipid outputs than steroid-free proliposomes. Size analysis and transmission electron microscopy showed an evidence of liposome formation within the nebuliser, which was followed by deaggregation and size reduction of multilamellar liposomes on nebulisation to a two-stage impinger. For each formulation, no difference in thermal transitions was observed between delivered liposomes and those remaining in the nebuliser. However, steroid (5 mole%) lowered the onset temperature and the enthalpy of the pretransition, and produced a similar onset temperature and larger enthalpy of the main transition, with broadened pretransition and main transitions. This indicates that BDP was entrapped and exhibited an interaction with the liposome phospholipid membranes. Since the pretransition was depressed but not completely removed and no phase separation occurred, it is suggested that the bilayers of the multilamellar liposomes can entrap more than 5 mole% BDP. Overall, liposomes were generated from proliposomes and DSC investigations indicated that the steroid was entrapped in the bilayers of aerosolised multilamellar vesicles.

Multi-kilowatt peak power nanosecond Er-doped fiber laser

We report a two-stage diode-pumped Er-doped fiber amplifier operating at the wavelength of 1550 nm at the repetition rate of 10-100 kHz with an average output power of up to 10 W. The first stage comprising Er-doped fiber was core-pumped at the wavelength of 1480 nm, whereas the second stage comprising double-clad Er/Yb-doped fiber was clad-pumped at the wavelength of 975 nm. The estimated peak power for the 0.4-nm full-width at half-maximum laser emission at the wavelength of 1550 nm exceeded 4-kW level. The initial 100-ns seed diode laser pulse was compressed to 3.5 ns as a result of the 34-dB total amplification. The observed 30-fold efficient pulse compression reveals a promising new nonlinear optical technique for the generation of high power short pulses for applications in eye-safe ranging and micromachining.

Medium-Chain-Length Poly (3-Hydroxyalkanoate) Nanoparticle Suspensions

Thesis (Master, Chemical Engineering) -- Queen's University, 2016-08-16 04:58:55.749

New Rigorous Decomposition Methods for Mixed-integer Linear and Nonlinear Programming

Process systems design, operation and synthesis problems under uncertainty can readily be formulated as two-stage stochastic mixed-integer linear and nonlinear (nonconvex) programming (MILP and MINLP) problems. These problems, with a scenario based formulation, lead to large-scale MILPs/MINLPs that are well structured. The first part of the thesis proposes a new finitely convergent cross decomposition method (CD), where Benders decomposition (BD) and Dantzig-Wolfe decomposition (DWD) are combined in a unified framework to improve the solution of scenario based two-stage stochastic MILPs. This method alternates between DWD iterations and BD iterations, where DWD restricted master problems and BD primal problems yield a sequence of upper bounds, and BD relaxed master problems yield a sequence of lower bounds. A variant of CD, which includes multiple columns per iteration of DW restricted master problem and multiple cuts per iteration of BD relaxed master problem, called multicolumn-multicut CD is then developed to improve solution time. Finally, an extended cross decomposition method (ECD) for solving two-stage stochastic programs with risk constraints is proposed. In this approach, a CD approach at the first level and DWD at a second level is used to solve the original problem to optimality. ECD has a computational advantage over a bilevel decomposition strategy or solving the monolith problem using an MILP solver. The second part of the thesis develops a joint decomposition approach combining Lagrangian decomposition (LD) and generalized Benders decomposition (GBD), to efficiently solve stochastic mixed-integer nonlinear nonconvex programming problems to global optimality, without the need for explicit branch and bound search. In this approach, LD subproblems and GBD subproblems are systematically solved in a single framework. The relaxed master problem obtained from the reformulation of the original problem, is solved only when necessary. A convexification of the relaxed master problem and a domain reduction procedure are integrated into the decomposition framework to improve solution efficiency. Using case studies taken from renewable resource and fossil-fuel based application in process systems engineering, it can be seen that these novel decomposition approaches have significant benefit over classical decomposition methods and state-of-the-art MILP/MINLP global optimization solvers.

The initial phase of sodium sulfite pulping of softwood : A comparison of different pulping options

Single stage and two-stage sodium sulfite cooking were carried out on either spruce, pine or pure pine heartwood chips to investigate the influence of several process parameters on the initial phase of such a cook down to about 60 % pulp yield. The cooking experiments were carried out in the laboratory with either a lab-prepared or a mill-prepared cooking acid and the temperature and time were varied. The influences of dissolved organic and inorganic components in the cooking liquor on the final pulp composition and on the extent of side reactions were investigated. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. A better understanding of the delignification mechanisms during bisulfite and acid sulfite cooking was obtained by analyzing the lignin carbohydrate complexes (LCC) present in the pulp when different cooking conditions were used. It was found that using a mill-prepared cooking acid beneficial effect with respect to side reactions, extractives removal and higher stability in pH during the cook were observed compared to a lab-prepared cooking acid. However, no significant difference in degrees of delignification or carbohydrate degradation was seen.  The cellulose yield was not affected in the initial phase of the cook however; temperature had an influence on the rates of both delignification and hemicellulose removal. It was also found that the  corresponding activation energies increased in the order:  xylan, glucomannan, lignin and cellulose. The cooking temperature could thus be used to control the cook to a given carbohydrate composition in the final pulp. Lignin condensation reactions were observed during acid sulfite cooking, especially at higher temperatures. The LCC studies indicated the existence of covalent bonds between lignin and hemicellulose components with respect to xylan and glucomannan. LCC in native wood showed the presence of phenyl glycosides, ϒ-esters and α-ethers; whereas the α-ethers  were affected during sulfite pulping. The existence of covalent bonds between lignin and wood polysaccharides might be the rate-limiting factor in sulfite pulping.